JP2000140635A - Heat stable metal oxide catalyst having perovskite crystal structure and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat stable high performance catalyst having perovskite crystal structure and the producing method. SOLUTION: The heat stable metal oxide catalyst having the perovskite crystal structure and expressed by a formula, AB1-xMxO3-δ, and the producing method and expressed by a formula, each of A and B represents a cation forming a fire resisting oxide, M represents a relatively non-volatile active cation and acts in the quantity of about 0.01-0.30 as a doping for the position B. Each of cations A, B and M is selected so that the quantity of oxygen defect expressed by (5) is at least 0.02. The catalyst exhibits excellent catalytic property after being aged at a temp. exceeding 1300 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thermally stable metal oxide catalyst having a perovskite crystal structure and a method for producing the same. In particular, the present invention relates to a highly active catalyst having a perovskite type structure having high resistance to heat aging and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION In conventional power generation by burning fossil fuels, natural gas is the most environmentally acceptable and produces large amounts of harmful nitrogen oxides (N
O _x ). These emissions can be substantially reduced by using a lean burn mixture and lowering the combustion temperature. However, a very active catalyst is needed to sustain the lean mixture combustion. Catalytic combustion allows the combustion (complete oxidation) of fuel / air mixtures of a very wide range of fuel concentrations and can even be used in explosive atmospheres.
However, lower fuel concentrations require more active catalysts. Needless to say, such a catalyst must be able to maintain its catalytic properties in a high-temperature environment.

The most active catalysts are those based on precious metals such as palladium and platinum. However, these catalysts are expensive and lose their catalytic properties at high temperatures exceeding 1000 ° C.

Polymetal oxides having a β-alumina structure and mainly containing aluminum oxide, alkaline earth oxides and / or lanthanum oxide and an active element which is generally manganese can be used even at high temperatures. Shows good catalytic activity. However, a major problem with using a material such as a catalyst is that the resistance to thermal shock is reduced when the self-supporting structure is used. This is mainly due to the two-dimensional thermal expansion coefficient of the above materials. Also, the production of these catalysts requires complicated methods.

Formula La _{1 -x} A _x MO ₃ (where A is Ca,
Alkaline earth metals such as Sr and Ba;
An oxide mainly composed of a transition metal having a perovskite crystal structure represented by a transition metal such as Co, Mn, Fe, and Ni exhibits high catalytic activity. A disadvantage of such catalysts is that the melting point is relatively low when the active transition metal is cobalt, manganese or iron. In high temperature environments, these catalysts often sinter and lose catalytic activity. These catalysts are stable up to about 800 ° C. Although the use of chromium as the active transition metal may give better results, chromates are also not suitable for temperatures above 1100 ° C. due to the volatility of chromium in the environment of the combustion products.
Similarly, metals in the platinum group may volatilize when used in place of the transition metal having a perovskite structure, and are more expensive.

The stability of the perovskite phase at high temperatures is
Such a phase is obtained by preparing a refractory oxide such as ZrO ₃ , TiO ₂ , La ₂ O ₃ , and Y ₂ O ₃ . The resulting catalyst has the general formula ABO ₃ (eg, SrZrO ₃ , S
rTiO ₃ , LaAlO ₃ ), and has a high melting point and excellent thermal stability. In particular, these perovskites, which have lower activity per se in terms of their refractory properties, have been proposed and tested as carrier materials for transition metal oxides. However, when using such materials, a reaction may take place between the two components and an inactive phase may be formed. Inactive phases can also occur when sintering occurs at the material surface. The melting points of these inactive phases are usually low.

US Pat. No. 4,126,580 shows perovskite catalysts having improved stability in a wide range of chemical environments. The elements included in the composition of these catalysts are selected so as to obtain a catalyst having a high lattice stability index. This is done by incorporating a metal with a low first ionization potential. However, a problem with many of these catalysts is that the catalyst activity appears to drop sharply above 1000 ° C.

US Pat. No. 4,110,251 discloses a perovskite-type crystal structure of the general formula ABO
_3-f X _f (wherein, X is fluorine or chlorine, f is about 0.1 to 1.0) Other catalyst composition represented by is described. Here, the oxygen deficiency caused by the presence of fluorine or chlorine increases the resistance of the composition to the reducing environment and increases the thermal stability. However, like the composition described in U.S. Pat. No. 4,126,580, the composition described in U.S. Pat. No. 4,110,251 does not appear to be suitable for temperatures above 1000.degree. It is.

[0009] U.S. Patent No. 5,712,220, suitable for use in the manufacture of components used in the oxygen separation device in the solid state, wherein _{Ln x A 'x' A "} x" B y B 'y _' B " _{y "}
O _{3 -z wherein} A ′ is a Group I element, A ″ is a Group I element,
Selected from Group II and Group III, wherein B, B ′ and B ″ are all transition metals, and the number Z is a number that neutralizes the charge of the compound). There is no definition of a component that is a refractory oxide at site B. Further, the catalysts described in U.S. Patent No. 5,712,220 are not suitable for catalytic combustion of hydrocarbons at high temperatures.

Accordingly, it is an object of the present invention to provide a thermally stable, high performance catalyst suitable for high temperature applications in relatively corrosive environments.

It is another object of the present invention to provide a catalyst that can withstand temperatures exceeding 1200 ° C. and can exhibit relatively good catalytic activity even at this temperature.

It is another object of the present invention to provide a catalyst represented by the general formula ABO ₃ and having an oxygen deficiency of at least about 0.02.

Yet another object of the present invention is to provide a simple method for producing a catalyst having a perovskite type structure, which can be molded into a self-supporting form or used on other refractory support materials. It is in.

[0014]

Specifically, according to the present invention, according to the general formula ABO ₃ (where A has an ionic radius of 0.0
A cation site occupied by at least one metal of 9 nm to 0.15 nm, and B has an ionic radius of 0.0
A cation site occupied by at least one metal that is between 5 nm and 0.10 nm, wherein the metal cations A and B
Are present in approximately the same theoretical ratios) and have a perovskite crystal structure, wherein the catalyst is of the formula ABO _{3- δ} wherein δ is at least about 0.02 Which is an amount of oxygen deficiency of the present invention.

In a preferred embodiment, the catalyst comprises a catalytic metal M, resulting in a catalyst of the formula AB _1-x M _x O _{3- δ} .

In a further preferred embodiment, the catalytic metal is a transition metal having an atomic number of 25 to 28, and x is about 0.3 or less.

In the most preferred embodiment, A is Ln, C
a, Sr and mixtures thereof, wherein B is Z
It is selected from r, Ce, Ti, Y, Al and mixtures thereof.

By selecting the elements in this way, a refractory and extremely active catalyst can be obtained.

According to another aspect of the present invention, a compound of general formula AB
_1-x M _x O _{3- δ} (where A is an ionic radius of 0.09 nm or more
B is a cation site occupied by at least one metal having a ionic radius of 0.05 nm to 0.15 nm.
0.10 nm is a cation site occupied by at least one metal, metal cations A and B are present in approximately the same stoichiometric ratio, δ is an oxygen deficiency of at least about 0.02, and M is A cation site occupied by at least one catalytic metal), and having a perovskite crystal structure. The precursor is mixed with a solution containing water, in the form of an oxide, hydroxide, carbonate, salt or any mixture thereof, and allowed to react to form an aqueous suspension of hydroxide particles. (A, B and M
Are each mixed in stoichiometric proportions such that δ is greater than about 0.02), b) drying the aqueous suspension to obtain dry particles, c) the drying And a method for producing a heat-stable metal oxide catalyst including a step of calcining the particles.

Other objects, advantages and features of the invention will emerge more clearly from a reading of the following description of a non-limiting preferred embodiment of the invention, given by way of example with reference to the accompanying tables. .

[0021]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a catalyst having a perovskite crystal structure and represented by the general formula ABO ₃ . These catalysts are further characterized in that both sites A and B contain a metal cation. The general formula above teaches that sites A and B are occupied by the same number of cations. An ideal perovskite structure is a cube with large cations occupying the corners of the cube and small cations occupying the center of the cube. Oxygen atoms are located at the center of each face of the cube. For this reason,
The cation from site A is coordinated with 12 oxygen atoms and the cation from site B is coordinated with 6 oxygen atoms. Other perovskite structures based on variations of the above structure are well known.

Cations from the A site are generally occupied by metal atoms having an ionic radius of 0.09 nm to 0.15 nm, while cations from the B site are generally occupied by metal atoms having an ionic radius of 0.05 nm to 0.10 nm. Occupied by atoms.

More specifically, the catalyst of the present invention comprises ZrO_Two,
TiO_Two, La_TwoO_Three, Y_TwoO_Three, CeO _Two, Al_TwoO_Three, Mg
Manufactured from refractory oxides such as O, CaO and SrO
With fire-resistant, highly stable perovskite
are doing. These perovskites have extremely high melting points
And extremely stable, but for complete oxidation of hydrocarbons
It is not good as a catalyst.

These perovskites having high fire resistance are:
By doping the B site with one or more transition metal cations M, it becomes catalytically active. Also, the cations at sites A and B are selected so that the amount of oxygen deficiency is at least about 2%. These two features of the present invention not only make the refractory catalyst very stable,
Even after high-temperature exposure, it can be made catalytically active.

The general formula of these refractory and extremely active catalysts having a perovskite structure is AB _1-x M _x O
_{3- δ} (δ ≧ 0.02). (Note that, for the purpose of clarifying the explanation, in the following formula describing the catalyst of the present invention, δ
, But should always be interpreted as suggesting δ. ) The doping of the B site with the transition metal must be well controlled for each thermal stability that one wishes to maintain. The estimated maximum level of doping at site B to maximize catalytic properties while maintaining thermal stability is about 30% in theory. About 1% as the minimum doping amount
Is required, in the above equation, 0.008 ≦ x ≦
0.32, preferably 0.01 ≦ x ≦ 0.30.

As a result of an experiment, it has been found that it is preferable to use a specific element in order to obtain a sufficient amount of oxygen deficiency, thermal stability at a high temperature, and good catalytic activity.
Cation A is preferably selected from the group consisting of lanthanum, calcium, strontium and mixtures thereof. In order to guarantee the optimal thermal stability of the catalyst according to the invention, the cation B is preferably selected from the group consisting of zirconium, cerium, titanium, yttrium, aluminum and mixtures thereof. As mentioned above, these cations are selected from the group capable of forming refractory and non-volatile oxides.

The catalyst metal cation for doping is preferably an element having an atomic number of 25 to 28, that is, manganese,
It is selected from the group consisting of iron, cobalt and nickel. These transition metals are correspondingly nonvolatile.

The catalyst of the present invention can be prepared first by mixing the precursors of the components of the particular perovskite composition. Cation A is preferably provided as a non-volatile oxide or carbonate. Cation B
Is preferably derived from a refractory oxide having extremely low volatility. The catalytic transition metal doping site B is
Preferably provided in the form of an aqueous solution of metal nitrate,
Oxides, carbonates or other salts can also be used.

All components are strictly mixed in stoichiometric proportions.
Mix the initial precursor suspension until a homogeneous suspension is obtained. Preferably, the particle size of the suspended particles is less than 1 μm. The suspension may be homogenized by kneading or high-speed mixing.

The suspension thus obtained is dried by freeze-drying or spray-drying, or any other method known in the art. By firing at a temperature lower than 1000 ° C., a perovskite phase is obtained.

[0031]

Example 1 Ca (Zr _0.92 Y _0.08 ) _0.9 Ni _0.1 O ₃
Production of calcium carbonate 20.00 g and yttria stabilization (8
wt%) Zirconia fine powder (Zircar Inc.)
22.50 g were charged into a 250 ml polyethylene bottle and stirred vigorously to obtain a suspension. To this mixture is introduced 65 ml of a solution containing 5.812 g of nickel dinitrate hexahydrate. Next, 100 ml of zirconia balls are added to the obtained suspension. After kneading the suspension for 2 hours, the suspension is poured into liquid nitrogen together with a grinding ball and rapidly frozen. The frozen material is then dried in a commercial freeze dryer under vacuum. Separate the balls from the sieved and dried precursor powder. The powder thus obtained is calcined in two stages without intermediate grinding. Finally, the obtained perovskite powder was added to 130
Aging at 0 ° C. for 7 hours.

[0032]

Example 2 Sr (Zr _0.92 Y _0.08 ) _0.9 Mn _0.1 O ₃
Preparation of 29.53 g of strontium carbonate 22.50 g of yttria-stabilized zirconia powder (Zircar Inc.)
Mix with. 65 ml of a solution containing 5.74 g of manganese dinitrate hexahydrate are introduced into the mixture. The suspension obtained is treated as described in Example 1.

[0033]

Example 3 Production of SrTi _0.9 Fe _0.1 O ₃ 36.908 g of strontium carbonate, 17.978 g of anatase (titanium dioxide) and gamma iron oxide (γFe
1.996 g of ₂ O ₃ ) are introduced into 75 ml of distilled water. The suspension obtained is treated as in the above example.

[0034]

Example 4 Production of SrTi _0.8 Fe _0.2 O ₃ 22.171 g of iron nitrate nonahydrate was dissolved in 80 ml of distilled water, and the solution was charged into a 250 ml polyethylene bottle. 17.534 g of anatase and 40.51 g of strontium carbonate are added to this solution in small portions. Sr
The addition of CO ₃ is achieved by an evolution of carbon dioxide. When this is stopped, the suspension obtained is treated in the same manner as in the above example.

[0035]

Example 5 Production of SrTi _0.8 Fe _0.1 Mn _0.1 O _{3 As} in Example 4 for producing SrTi _0.8 Fe _0.2 O ₃ ,
36.908 g of strontium carbonate and anatase 1
A mixture of 5.980 g and 1.998 g of gamma iron oxide is
All the mechanical and thermal operations described in the above examples are carried out after the addition in small portions to a solution containing 7.176 g of manganese nitrate hexahydrate.

[0036]

Example 6 Production of SrTi _0.9 Co _0.1 O _{3 As} in Example 5, 29.526 g of strontium carbonate sufficiently mixed with 14.380 g of anatase, and an aqueous solution containing 5.821 g of dissolved cobalt nitrate hexahydrate 75
Add in small portions to ml. Here too, the suspension obtained is treated in the same way as in the above example.

[0037]

Example 7 Production of LaAl _0.9 Co _0.1 O ₃ 16.455 g of lanthanum oxide charged in a 250 mL polyethylene bottle was moistened with 25 mL of distilled water. After about 2 hours required to complete the exothermic reaction to form lanthanum hydroxide, aluminum trinitrate nonahydrate.
70 mL of a solution containing 11 g and 2.911 g of cobalt dinitrate hexahydrate was added with vigorous stirring. The rapidly gelling mixture was kneaded with zirconia balls for at least 15 minutes, then processed by freeze drying and calcined at 700 ° C. for several hours.

[0038]

Embodiment 8 La _0.85 Sr _0.15 Al _0.88 Fe _0.12 O ₃
Production of 6.343 g of strontium nitrate was dissolved in 25 mL of distilled water. Using this solution, 27.97 g of lanthanum oxide was moistened and left to react for about 2 hours to form lanthanum hydroxide. 66.02 g of aluminum trinitrate nonahydrate was dissolved in 100 mL of distilled water, and this solution was charged into a 500 mL polyethylene bottle. In this solution, 1.9164 g of gamma iron oxide was dissolved. Then, a strong suspension of lanthanum hydroxide was quickly introduced with vigorous stirring. The mixture gelled in a few minutes was added to the zirconia ball (1
(50 mL) for 3 hours.

[0039]

Embodiment 9 La _0.85 Sr _0.15 Al _0.87 Fe _0.09 Co
Production of _0.04 O ₃ This catalyst was produced in the same manner as in Example 8.
However, in this example, boehmite was used instead of aluminum nitrate. Strontium nitrate 6.343
g was dissolved in 25 mL of distilled water. The solution was poured onto 27.97 g of lanthanum oxide, which was completely wetted. About 2
Over time, the lanthanum oxide was converted to lanthanum hydroxide by an exothermic reaction. The suspension was prepared by dissolving 11.51 g of boehmite in 65 mL of a solution containing 7.27 g of iron nitrate nonahydrate and 2.328 g of cobalt nitrate hexahydrate and held in a 250 mL polyethylene bottle. A suspension was introduced. To this mixture, zirconia balls for grinding 100 m
L was added and the suspension was kneaded for 3 hours. The final suspension was treated in the same manner as in the above-mentioned example to obtain a perovskite catalyst.

[0040]

Comparative Example 1 Production of Sr _0.8 La _0.2 MnAl ₁₁ O _{19- δ} 30.5 g of boehmite thoroughly mixed with 1.645 g of lanthanum oxide in a 250 mL bottle made of polyethylene
Was added to strontium nitrate (8.4567 g), manganese nitrate (14.35 g), and crushed zirconia balls (100 mL).
Was added to 70 mL of a solution containing This mixture is
The mixture was kneaded for a time, and then processed in the same manner as in the other examples.
Upon firing at 1100 ° C. for 12 hours, a β-alumina structure was formed.

[0041]

Comparative Examples 2 to 4 For comparison purposes, International Patent Application Publication No. W
According to the method described in O97 / 48641, three kinds of perovskite compositions containing only a transition metal as a main component, that is, LaMnO ₃ and La _0.8 Sr having the following components:
_0.2 MnO ₃ , La _0.66 Sr _0.34 Ni _0.3 Co _0.7 O ₃ were produced.

For the production of La _0.8 Sr _0.2 MnO _3, 26.4 g of lanthanum oxide (La ₂ O ₃ ), 8.465 g of strontium nitrate and 56.41 of manganese dinitrate hexahydrate were used.
using the g, for the production of LaMnO _3, lanthanum oxide (L
a ₂ O ₃₎ 33g and secondary manganese nitrate hexahydrate 56.4
1 g of lanthanum oxide (La ₂ O ₃ ) for the production of La _0.66 Sr _0.34 Ni _0.3 Co _0.7 O ₃ .
20.373 g of cobalt nitrate hexahydrate, 8.724 g of nickel nitrate hexahydrate and 7.19 of strontium nitrate
5 g were used.

12 hours at 590 ° C., and 4 hours at 640 ° C.
After calcining for hours, the specific surface area was 10 m ² / g, and the catalytic activity was extremely high. For comparison with the catalyst of the present invention,
The perovskite of this example was aged in air at 1070 ° C. for 26 hours. This aging reduced the specific surface area to about 0.6 m ² / g.

[0044]

Example 10 Use of the Catalyst of the Invention in Catalytic Combustion of Methane The catalytic activity of the catalysts of Examples 1 to 9 was tested in a laboratory tubular reactor consisting of 1.3 cm inner diameter alumina ceramic tubes. The activity was perovskite mainly composed of a transition metal (no refractory oxide at the B site), LaM
nO ₃ , La _0.8 Sr _0.2 MnO ₃ , La _0.66 Sr _0.34 Ni
_0.3 Co _0.7 O ₃ activity and β-alumina ie Sr _0.8 L
The activity was compared with the activity of a _0.2 MnAl ₁₁ O _{19- δ} .

Pumice (particles having a particle size of 350 to 500 μm) 1
A catalyst bed of 1 g of the catalyst powder diluted (mixed) with 0 ml is provided with a thermocouple alumina sheath (diameter of 0. 0) passing through the reactor tube and the center.
64 cm). 2 in the air
% Of methane was passed over the catalyst at 400 ml / min. The reactor was heated stepwise to about 50 ° C. When the temperature stabilizes, water is removed with a desiccant, and in the case of methane and carbon dioxide, Porapak
The effluent was analyzed by gas chromatography using a Q column.

Table 1 below shows specific conversions for 2% methane in air over the catalysts of the present invention and other perovskites based solely on transition metals containing no refractory oxides at the B site. (10%, 50% and 90%) at which point the temperature was obtained. All catalysts are 1070 ° C
For 26 hours.

[0047]

[Table 1]

From Table 1, it can be seen that the specific surface area (SSA) and catalytic activity of the five catalysts according to the invention are greater than those of the catalysts based solely on transition metals. It will be appreciated that the catalyst of the present invention has a lower temperature to 90% conversion of methane than the catalyst without refractory oxides.
Even at 10% methane conversion, the catalyst of the present invention showed very good catalytic activity.

Table 2 shows that for 2% methane in air,
Shown are the temperatures at which specific conversions (10%, 50% and 90%) were obtained on the catalyst of the invention. Β
-Compare with results obtained with catalysts having an alumina structure. All catalysts were aged at 1070 ° C. for 4 hours and 1300 ° C. for 7 hours.

[0050]

[Table 2]

From the results in Table 2, it can be seen that the catalytic activity of the catalyst according to the invention is equal to or better than the best catalytic activity of β-alumina known in the prior art. The main advantage of the catalyst according to the invention compared to β-alumina lies in the isosteric coefficient of thermal expansion, which is believed to be a factor that increases the resistance to thermal shock. Another advantage is that the manufacturing method is simple.

Table 3 also shows that for 2% methane in air,
Figure 3 shows the temperature at which a certain conversion is obtained on some of the catalysts of the last example. Again, the results obtained are compared with those obtained with the same catalyst having a β-alumina structure. These catalysts were treated at 1300 ° C. for 7 hours for 14 hours.
Aged at 50 ° C. for 6 hours.

[0053]

[Table 3]

Table 3 shows that some of the catalysts of the present invention contained 130
It can be seen that after aging at temperatures above 0 ° C., some have better catalytic activity than the best β-alumina.

Although the present invention has been described with reference to preferred embodiments of the invention, modifications may be made without departing from the spirit and essence of the inventive subject matter as defined in the appended claims.

[0056]

According to the present invention, a thermally stable high-performance catalyst suitable for use at a high temperature in a relatively corrosive environment can be obtained. A catalyst that can withstand and exhibit relatively good catalytic activity even at this temperature can be obtained.

Further, according to the present invention, there is provided a catalyst represented by the general formula ABO ₃ having an oxygen deficiency of at least about 0.02, having a perovskite type structure, and being formed into a self-supporting form or other A simple method is provided for producing a catalyst that can be used on a refractory support material.

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Claims (28)

[Claims] 1. The formula ABO _{3 wherein} A is a cation site occupied by at least one metal ion having an ionic radius of 0.09 nm to 0.15 nm, and B is an ionic site having a ionic radius of 0.05 nm. Cation site occupied by at least one metal ion of about 0.10 nm, wherein metal cations A and B are present in approximately the same stoichiometric ratio) and have a perovskite crystal structure In an oxide catalyst, the catalyst has the formula ABO _{3- δ}
(Where δ is an oxygen deficiency of at least 0.02)
An improved heat-stable metal oxide catalyst represented by the formula: 2. A method according to claim 1, wherein the metal cation B is doped with at least one catalytic metal represented by M,
2. The thermally stable metal oxide catalyst according to claim 1, which provides a catalyst represented by M) O3 _{- δ} . 3. The heat-stable metal oxide catalyst according to claim 2, wherein the at least one catalyst metal M is selected from the group consisting of elements having atomic numbers of 25 to 28. 4. The method according to claim 1, wherein the metal cation B is 0.01 to 0.30.
4. The heat of claim 3 which provides a catalyst doped with an amount of and having the general formula AB _1-x M _x O _{3- δ wherein} 0.01 ≦ x ≦ 0.30. Stable metal oxide catalyst. 5. The thermostable metal oxide catalyst according to claim 1, wherein the metal cation A is selected from the group consisting of lanthanum, calcium, strontium and mixtures thereof. 6. The thermally stable metal oxide catalyst according to claim 4, wherein the metal cation A is selected from the group consisting of lanthanum, calcium, strontium and mixtures thereof. 7. The thermostable metal oxide catalyst according to claim 1, wherein the metal cation B is selected from the group consisting of zirconium, cerium, titanium, yttrium, aluminum and mixtures thereof. 8. The heat-stable metal oxide catalyst according to claim 4, wherein the metal cation B is selected from the group consisting of zirconium, cerium, titanium, yttrium, aluminum and mixtures thereof. 9. The thermally stable metal oxide catalyst according to claim 6, wherein the metal cation B is selected from the group consisting of zirconium, cerium, titanium, yttrium, aluminum and mixtures thereof. 10. The formula SrZr _1-x M _x O _{3- δ} (where x ≦
10. The heat-stable metal oxide catalyst according to claim 9, wherein the catalyst is 0.3. 11. The formula CaZr _1-x M _x O _{3- δ} (where x ≦
10. The heat-stable metal oxide catalyst according to claim 9, wherein the catalyst is 0.3. 12. The formula SrTi _1-x M _x O _{3- δ} (where x ≦
10. The heat-stable metal oxide catalyst according to claim 9, wherein the catalyst is 0.3. 13. The thermally stable metal oxide catalyst according to claim 12, wherein M is iron (Fe). 14. M is iron (Fe) and manganese (M
13. A mixture of n) or cobalt (Co).
3. The heat-stable metal oxide catalyst according to 1.). 15. Formula _{La 1-y Sr y Al 1} -x M x O 3- δ ( wherein, a x ≦ 0.3, a is y ≦ 0.3) represented by the claims 9 3. The heat-stable metal oxide catalyst according to 1. 16. The thermally stable metal oxide catalyst according to claim 15, wherein M is iron (Fe). 17. M is iron (Fe) and manganese (M
16. A mixture of n) or cobalt (Co).
3. The heat-stable metal oxide catalyst according to 1.). 18. A general formula ABMO _{3- δ wherein} A is a cation site occupied by at least one metal ion having an ionic radius of 0.09 nm to 0.15 nm;
Is a cation site occupied by at least one metal ion having an ionic radius of 0.05 nm to 0.10 nm, wherein metal cations A and B are present in almost the same theoretical ratio, and δ is at least 0.02. Oxygen deficiency, M
Is a cation site occupied by at least one catalytic metal) and comprises a perovskite crystal structure, comprising: a) each metal cation A, B and M Is mixed with a solution containing water in the form of an oxide, hydroxide, carbonate, salt or any mixture thereof and reacting to form an aqueous suspension of hydroxide particles. (A, B and M
Are each mixed in a stoichiometric ratio so that the total oxygen deficiency is at least about 0.02); b) drying the aqueous suspension to obtain dry particles; c. And b) calcining the dried particles. 19. The process according to claim 18, wherein the calcination step c) is performed at a temperature below 1000 ° C. 20. The method according to claim 18, wherein the catalyst metal M is selected from the group consisting of elements having atomic numbers of 25 to 28. 21. The method according to claim 20, wherein the precursor of the metal cation M is a salt. 22. The method according to claim 21, wherein the salt is a nitrate. 23. The method of claim 18, wherein the metal cation A is selected from the group consisting of lanthanum, calcium, strontium, and mixtures thereof, and wherein the precursor form is an insoluble oxide or carbonate. A method for producing a metal oxide catalyst. 24. The method of claim 22, wherein the metal cation A is selected from the group consisting of lanthanum, calcium, strontium, and mixtures thereof, and wherein the precursor form is an insoluble oxide or carbonate. A method for producing a metal oxide catalyst. 25. The method according to claim 18, wherein the metal cation B is selected from the group consisting of zirconium, cerium, titanium, yttrium, aluminum and mixtures thereof, the precursor form of which is an insoluble oxide or a soluble salt. A method for producing a thermally stable metal oxide catalyst. 26. The method according to claim 23, wherein the metal cation B is selected from the group consisting of zirconium, cerium, titanium, yttrium, aluminum and mixtures thereof, the precursor form of which is an insoluble oxide or a soluble salt. A method for producing a thermally stable metal oxide catalyst. 27. The method of claim 24, wherein the metal cation B is selected from the group consisting of zirconium, cerium, titanium, yttrium, aluminum and mixtures thereof, and wherein the precursor form is an insoluble oxide or soluble salt. A method for producing a thermally stable metal oxide catalyst. 28. Use of the catalyst according to any one of claims 1 to 17 for burning hydrocarbons.